CN109851469A - A kind of method that methanol anaerobic dehydrogenation prepares styrene with Benzyl Side-Chain alkylation coupling reaction - Google Patents
A kind of method that methanol anaerobic dehydrogenation prepares styrene with Benzyl Side-Chain alkylation coupling reaction Download PDFInfo
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Abstract
The invention discloses a kind of methods that methanol anaerobic dehydrogenation and Benzyl Side-Chain alkylation coupling reaction prepare styrene；Containing toluene and methanol unstripped gas is passed through reactor in the method to contact with bifunctional catalyst, methanol first occurs anaerobic dehydrogenation reaction and generates formaldehyde, and gained formaldehyde occurs side chain alkylation again with toluene and reacts generation styrene.Toluene conversion, use ratio of methanol and styrene yield can be improved by two reactions mutually coupling in this method.
Description
Technical field
The present invention relates to a kind of methods that methanol anaerobic dehydrogenation and Benzyl Side-Chain alkylation coupling reaction prepare styrene, belong to
In catalytic field.
Background technique
Important monomer of the styrene as polymer, mainly for the production of polystyrene (PS), acrylonitrile-butadiene resin
(ABS), the chemical products such as expansible polystyrene (EPS), SBR styrene butadiene rubbers (SBR).Traditional production of styrene skill
Art is ethylbenzene dehydrogenation method, mainly obtains purpose product styrene, the party by Friedel-Craft reaction, catalytic dehydrogenating reaction
That there is process routes is long for method, equipment investment is big, side reaction is more, energy consumption is high, depends on a series of problems, such as petroleum resources unduly.Cause
This, new styrene Production has obtained the extensive concern of people.
Japanese researchers Sidorenko in 1967 et al. (Dokl.Akad.NaukSSSR, 1967,173 (1): 132-134)
Methylbenzene methanol side chain alkylation preparation of styrene reaction in alkali metal ion exchange X-type molecular sieve is reported for the first time, with ethylbenzene dehydrogenation
Raw material sources are extensive, omit dehydrogenation step, energy consumption reduces, cost reduces and select methanol as alkylation examination compared to having for method
Agent reduces the advantages such as dependence, reduction environmental pollution to petroleum resources, has potential application prospect.However, the process route
Remain toluene conversion is low, the serious utilization rate of Methanol Decomposition is low, resultant styrene is selectively low, ethyl-benzene level is higher etc.
Problem hinders the further industrial application of methylbenzene methanol side chain alkylation technique.
Summary of the invention
According to an aspect of the invention, there is provided a kind of methanol anaerobic dehydrogenation and Benzyl Side-Chain are alkylated coupling reaction system
The method of standby styrene, can effectively improve toluene conversion and use ratio of methanol, while improving styrene yield；It solves
Methylbenzene methanol side chain alkylation reaction at present prepares low-conversion present in styrene, low selectivity problem.
The method that a kind of methanol anaerobic dehydrogenation and Benzyl Side-Chain alkylation coupling reaction prepare styrene, feature exist
In including at least: the unstripped gas containing methanol and toluene being passed through reactor, is contacted with catalyst, reacts, prepares the benzene second
Alkene；
The catalyst includes dehydrogenation and alkaline molecular sieve；
The molar ratio of toluene and methanol is 0.1~10:1 in the unstripped gas；The reaction temperature is 300~600 DEG C, instead
Answering pressure is 0.1~10MPa；The toluene and methanol feedstock gas gross mass air speed are 0.1~6h-1。
Optionally, the molar ratio upper limit of toluene and methanol is selected from 0.2:1,1:3,1:1,3:1,6:1,9 in the unstripped gas:
1 or 10:1；Lower limit is selected from 0.1:1,0.2:1,1:3,1:1,3:1,6:1 or 9:1.
Optionally, the reaction temperature upper limit is selected from 350 DEG C, 380 DEG C, 420 DEG C, 460 DEG C, 500 DEG C or 600 DEG C；Lower limit
Selected from 300 DEG C, 350 DEG C, 380 DEG C, 420 DEG C, 460 DEG C or 500 DEG C.
Optionally, described the reaction pressure upper limit 0.1MPa, 0.5MPa, 1.0MPa, 2.0MPa or 10MPa；Lower limit is selected from
0.1MPa, 0.5MPa, 1.0MPa or 2.0MPa.
Optionally, the toluene and the methanol feedstock gas gross mass air speed upper limit are selected from 0.2h-1、1h-1、3h-1、5h-1Or 6h-1；Lower limit is selected from 0.1h-1、0.2h-1、1h-1、3h-1Or 5h-1。
Optionally, the molar ratio of toluene and methanol is 0.2~9:1 in the unstripped gas；The reaction temperature be 350~
500 DEG C, reaction pressure is 0.1~2MPa；The toluene and methanol feedstock gas gross mass air speed are 0.2~5h-1。
It optionally, include that at least one contains the catalyst bed of the catalyst in the reactor.
The mass ratio of the alkaline molecular sieve and dehydrogenation is 0.1~10:1.
Optionally, the quality of the alkaline molecular sieve and dehydrogenation is selected from 1:2,2:1,4:1,6:1,8:1 than the upper limit
Or 10:1；Lower limit is selected from 0.1:1,1:2,2:1,4:1,6:1 or 8:1.
Optionally, the mass ratio of the alkaline molecular sieve and dehydrogenation is 0.5~5:1.
Optionally, the dehydrogenation is selected from alkali metal infusibility salt, load metal oxide, metal ion exchanged
At least one of molecular sieve.
The alkali molecules are screened from least one of alkaline molecular sieve.
Optionally, the catalyst, including dehydrogenation, alkaline molecular sieve；
The dehydrogenation be selected from alkali metal infusibility salt, load metal oxide, metal ion exchanged molecular sieve
In at least two, the molecular sieve of load metal oxide or metal ion exchanged；
The alkali molecules are screened from least one of alkaline molecular sieve；
The mass ratio of the alkaline molecular sieve and dehydrogenation is 0.1~10:1.
Optionally, the mass loading amount of metal oxide is 10~30% in the load metal oxide.
Optionally, in the load metal oxide metal oxide the mass loading amount upper limit be selected from 15%, 20%,
25% or 30%；Lower limit is selected from 10%, 15%, 20% or 25%.
Optionally, the alkali metal infusibility salt is alkali metal infusibility salt compound by grinding, is dried, roasting obtains institute
State alkali metal infusibility salt；
The alkali metal infusibility salt compound is selected from least one of sodium carbonate, Boratex, sodium molybdate；
The carrier of the load metal oxide is SiO2, metal oxide be selected from copper oxide, silver oxide,
At least one of the oxide of zinc, oxide of zirconium；
Metal ion is selected from sodium ion, copper ion, cerium ion, manganese ion and magnesium in the molecular sieve of the metal ion exchanged
At least one of ion；The molecular sieve is ZSM-5 molecular sieve.
Optionally, at least one in the alkali molecules FAU structure molecular screen modified screened from alkali metal ion exchange
Kind；Wherein, in the modified FAU structure molecular screen of the alkali metal ion exchange, the exchange degree of alkali metal ion is 20~90%.
Optionally, the exchange degree upper limit of the alkali metal ion be selected from 23.1%, 29.8%, 51.3%, 56.1%,
58.8%, 60.9%, 62.3%, 63.2%, 63.3%, 68.7% or 90%；Lower limit be selected from 20%, 23.1%, 29.8%,
51.3%, 56.1%, 58.8%, 60.9%, 62.3%, 63.2%, 63.3% or 68.7%.
Optionally, the alkali metal ion is selected from least one of potassium ion, rubidium ion, cesium ion；The FAU structure
Molecular sieve is selected from least one of X-type molecular sieve, Y type molecular sieve.
Optionally, the alkali metal infusibility salt is alkali metal infusibility salt compound through 110~130 DEG C of drying, 500~650
DEG C roasting 1~6h preparation.
Optionally, the sial atomic molar ratio of the FAU structure molecular screen is 1~10.
Optionally, the sial atomic molar of the FAU structure molecular screen than the upper limit be selected from 1.17,2.89,4.53,5.54,
8.98,9.79 or 10；Lower limit is selected from 1,1.17,2.89,4.53,5.54,8.98 or 9.79.
Optionally, the alkaline molecular sieve is alkali metal type X-type molecular sieve and/or Y type molecular sieve, and alkali metal element is selected from
K, at least one of Rb, Cs.
Optionally, the preparation method of the bifunctional catalyst, which is characterized in that at least include the following steps:
(a) dehydrogenation is obtained；
(b) alkaline molecular sieve is obtained；
(c) by dehydrogenation and alkaline molecular sieve ball milling 2~20 hours on ball mill respectively, uniform progress is remixed
Shaping of catalyst；Or
By the mixture containing dehydrogenation and alkaline molecular sieve, urged again within ball milling 2~20 hours on ball mill
Agent molding.
Optionally, dehydrogenation described in step (a) is selected from alkali metal infusibility salt, load metal oxide, metal
At least one of molecular sieve of ion exchange；
The preparation method of the load metal oxide includes deposition-precipitation method or equi-volume impregnating；
The preparation method of the molecular sieve of metal ion exchanged includes: molten using metal salt presoma in the dehydrogenation
Liquid carries out ion exchange to molecular sieve, filters, washing, drying, and roasting obtains the molecular sieve of the metal ion exchanged；
The preparation method of alkaline molecular sieve described in step (b) includes: using alkali metal salt precursor solution to molecular sieve
Ion exchange is carried out, is filtered, washing, drying, roasting obtains the alkaline molecular sieve.
Optionally, the metal cation salt presoma is one of nitrate or/and acetate of respective metal.
Optionally, the upper limit of concentration of the metal salt precursor solution is selected from 0.3mol/L, 0.4mol/L or 0.6mol/L；
Lower limit is selected from 0.2mol/L, 0.3mol/L or 0.4mol/L.
Optionally, the concentration of the metal salt precursor solution is 0.2~0.6mol/L.
Optionally, the upper limit of concentration of the alkali metal salt precursor solution is selected from 0.3mol/L, 0.4mol/L or 0.6mol/
L；Lower limit is selected from 0.2mol/L, 0.3mol/L or 0.4mol/L.
Optionally, the concentration of the alkali metal salt precursor solution is 0.2~0.6mol/L.
Optionally, the precipitation method are deposited after generating precipitating under precipitating reagent effect by the soluble-salt of respective metal
It is made on carrier.The soluble-salt preferably nitrate or acetate, the precipitating reagent be selected from sodium carbonate, sodium bicarbonate,
At least one of ammonium carbonate, ammonium hydroxide or potassium carbonate.
As a kind of specific embodiment, the preparation step of the deposition-precipitation method is as follows:
(a) under 55~90 DEG C of stirring conditions, precipitating reagent is added in the suspension of Xiang Hanyou metal soluble-salt and carrier；
(b) at 75~85 DEG C after aging at least 5h, isolated solid, by 110~130 DEG C of drying, 500~650
DEG C roasting 1~6h to get arrive the load metal oxide.
As a kind of specific embodiment, steps are as follows for the equi-volume impregnating:
By the maceration extract containing metal ion to carrier carry out incipient impregnation after, by 110~130 DEG C drying, 500~
650 DEG C of 1~6h of roasting to get arrive the load metal oxide.
As a kind of specific embodiment, the ZSM-5 molecular sieve preparation step of the metal ion exchanged is as follows: respectively
Ion friendship is carried out to certain mass ZSM-5 molecular sieve with 0.2~0.6mol/L metal nitrate or/and acetate precursor solution
It changes, solid-to-liquid ratio is exchanged for 4h at 80 DEG C when being 10:1,550 DEG C of roastings in Muffle furnace by obtained solid after filtering, wash, being dry
6h is burnt, is then repeated 2 times process to get the ZSM-5 molecular sieve of metal ion exchanged is arrived.
As a kind of specific embodiment, the alkali metal type X-type molecular sieve or Y type molecular sieve preparation step are as follows:
0.2~0.6mol/L alkali nitrates precursor solution is respectively adopted, ion is carried out to certain mass NaX or NaY type molecular sieve
Exchange, solid-to-liquid ratio exchange 4h at 80 DEG C when being 10:1, obtained solid roasts at 550 DEG C in Muffle furnace after filtering, wash, being dry
6h is burnt, is then repeated 2 times the process to get alkali metal type X-type molecular sieve or Y type molecular sieve is arrived.
As a kind of specific embodiment, the methanol anaerobic dehydrogenation and Benzyl Side-Chain alkylation coupling reaction prepare benzene
The method of ethylene carries out in fixed bed reactors, and step is summarized as follows: the desired amount of catalyst being taken to be placed in reactor constant temperature
After quartz sand is loaded at both ends, 1~2h is activated 400~650 DEG C at a temperature of by area under helium atmosphere for catalyst.Then cool down
To reaction temperature and reaction pressure is set, the toluene prepared in proportion and carbinol mixture micro pump are injected into preheater, with
It is passed through reactor after carrier gas mixing, with bifunctional catalyst haptoreaction, reaction product is analyzed using gas chromatograph.
In the present invention, partial size unit " mesh " refers to that per inch is apart from interior eyelet number on the sieve for sieving different-grain diameter
Mesh.Such as 20 mesh just refer to that the eyelet on per inch is 20 sieves, 20~40 mesh are the sieves referred to through 20 mesh
The partial size retained by the sieve of 40 mesh.
Catalyst of the present invention is bifunctional catalyst, compound with alkaline molecular sieve catalyst by dehydrogenation,
On the one hand the reaction rate that methanol dehydrogenation generates formaldehyde process can be improved, inhibit the generation of Methanol Decomposition side reaction, improve first
The utilization rate of alcohol, gained formaldehyde are reacted as real alkylating reagent with toluene, can further improve toluene conversion, are increased
Pendant alkyl group rate improves styrene yield；On the other hand, the addition of dehydrogenation effectively inhibits toluene and methanol
Phenyl ring alkylated reaction reduces the generation of the by-products such as dimethylbenzene and more toluene.
The beneficial effect that the present invention can generate includes:
(1) method that the present invention prepares styrene using methanol anaerobic dehydrogenation and Benzyl Side-Chain alkylation coupling reaction, can
To improve toluene conversion, use ratio of methanol, resultant styrene selectivity；
(2) bifunctional catalyst provided by the present invention has preferable stability, continuous to transport on fixed bed reactors
Row 500h there are no apparent deactivation phenomenom；
(3) methanol anaerobic dehydrogenation provided by the present invention and Benzyl Side-Chain alkylation coupling reaction prepare the side of styrene
Method, it is easy to operate, meet industrial application requirement, is convenient for large-scale industrial production.
Specific embodiment
The present invention is described in detail below with reference to embodiment, but the invention is not limited to these embodiments.
Unless otherwise instructed, the raw material in the embodiment of the present invention and catalyst are bought by commercial sources.
Toluene conversion, use ratio of methanol and styrene yield are counted according to following formula in the embodiment of the present invention
It calculates:
Embodiment 1: the preparation of alkaline molecular sieve
Molecular sieve employed in embodiment is all from commercially available.
The preparation of alkali metal ion modified X-type, Y type molecular sieve:
20g NaX or NaY molecular sieve are taken, the forerunners such as 0.2~0.6mol/L potassium nitrate, rubidium nitrate, cesium nitrate are respectively adopted
Liquid solution carries out ion exchange to molecular sieve, and solid-to-liquid ratio exchanges 4h at 80 DEG C when being 10:1, gained after filtering, wash, being dry
Solid roasts 6h in Muffle furnace at 550 DEG C, be then repeated 2 times the process, obtains alkali metal type X-type, Y type molecular sieve, sample
It is H-1 that product are numbered respectively#~H-6#。
Gained sample number into spectrum, precursor solution type and concentration and ion-exchange degree are as shown in table 1.Using XRF element
Analyzer (the Axios 2.4KW type of PANAbalytical company) carries out elemental analysis, ion-exchange degree root to acquired sample
It is calculated according to the sodium content of exchange front and back sample, calculation formula are as follows:
Ion-exchange degree=100% × (in the preceding molecular sieve of exchange after molar content-exchange of Na element in molecular sieve
The molar content of Na element)/exchange before in molecular sieve Na element molar content.
Table 1
| Sample number into spectrum | Molecular sieve | Precursor solution and concentration | Ion-exchange degree/% |
| H-1# | NaX (Si/Al=1.17) | 0.4mol/L potassium nitrate | 62.3 |
| H-2# | NaX (Si/Al=1.17) | 0.4mol/L rubidium nitrate | 56.1 |
| H-3# | NaX (Si/Al=1.17) | 0.4mol/L cesium nitrate | 51.3 |
| H-4# | NaY (Si/Al=2.89) | 0.4mol/L potassium nitrate | 68.7 |
| H-5# | NaY (Si/Al=2.89) | 0.4mol/L rubidium nitrate | 63.2 |
| H-6# | NaY (Si/Al=2.89) | 0.4mol/L cesium nitrate | 58.8 |
| H-7# | NaX (Si/Al=4.53) | 0.2mol/L rubidium nitrate | 23.1 |
| H-8# | NaX (Si/Al=8.98) | 0.6mol/L cesium nitrate | 60.9 |
| H-9# | NaY (Si/Al=5.54) | 0.2mol/L rubidium nitrate | 29.8 |
| H-10# | NaY (Si/Al=9.79) | 0.6mol/L cesium nitrate | 63.3 |
Embodiment 2: the preparation of dehydrogenation
Alkali metal infusibility salt preparation: alkali metal infusibility salt in sodium carbonate, Boratex, sodium molybdate, sodium metaaluminate extremely
Few one kind.Alkali metal infusibility salt is ground first, then through 110 DEG C of drying, 550 DEG C of roasting 6h.Obtain alkali metal infusibility
Salt, sample number into spectrum DE-1#~DE-6#。
Gained sample number into spectrum, alkali metal infusibility salt type and mixed proportion are as shown in table 2.Wherein mixed proportion is according to alkali
Metal infusibility salt quality calculates.
| Sample number into spectrum | Alkali metal infusibility salt type | Mixed proportion |
| DE-1# | Sodium carbonate | -- |
| DE-2# | Boratex | -- |
| DE-3# | Sodium molybdate | -- |
| DE-4# | Sodium carbonate+Boratex | 1:2 |
| DE-5# | Sodium carbonate+sodium molybdate | 1:1 |
| DE-6# | Sodium carbonate+Boratex | 2:1 |
Load metal oxide carrier is SiO2, metal oxide be selected from copper oxide, silver oxide, zinc oxygen
At least one of compound, oxide of zirconium.Load metal oxide preparation method is deposition-precipitation method or incipient impregnation
Method.
Deposition-precipitation method prepares the step of load metal oxide and includes:
(a) under 80 DEG C of stirring conditions, precipitating reagent is added in the suspension of Xiang Hanyou metal soluble-salt and carrier；
(b) at 80 DEG C after aging at least 5h, isolated solid is arrived by 130 DEG C of drying, 550 DEG C of roasting 6h
Load metal oxide, sample number into spectrum DE-7#~DE-13#。
Equi-volume impregnating prepares the step of load metal oxide are as follows: by the maceration extract containing metal ion to load
After body carries out incipient impregnation, load metal oxide, sample number into spectrum are arrived by 110 DEG C of drying, 550 DEG C of roasting 6h
For DE-14#~DE-16#。
Gained sample number into spectrum, load metal oxide type, preparation method and mixed proportion are as shown in table 3.Wherein
Mixed proportion is according to load metal oxide Mass Calculation.
Table 3
In the ZSM-5 molecular sieve of metal ion exchanged, metal ion be selected from sodium ion, copper ion, cerium ion, manganese ion,
At least one of magnesium ion, preparation step are as follows:
5g ZSM-5 molecular sieve is taken, molecular sieve is carried out with 0.2~0.6mol/L metal nitrate precursor solution respectively
Ion exchange, solid-to-liquid ratio are exchanged for 4h at 80 DEG C when being 10:1, after filtering, wash, being dry by obtained solid in Muffle furnace
Process, is then repeated 2 times by 550 DEG C of roasting 6h, obtains the ZSM-5 molecular sieve of metal ion exchanged, and gained sample number into spectrum is DE-
17#~DE-24#。
Gained sample number into spectrum, molecular sieve type and mixed proportion are as shown in table 4.Wherein mixed proportion is according to ion exchange
Liquid concentration calculation.
Table 4
| Sample number into spectrum | Molecular sieve type | Precursor solution and concentration |
| DE-17# | Na-ZSM-5 | 0.2mol/LNaNO3 |
| DE-18# | Cu-ZSM-5 | 0.4mol/L Cu(NO3)2 |
| DE-19# | Ce-ZSM-5 | 0.4mol/L Ce(NO3)3 |
| DE-20# | Mn-ZSM-5 | 0.6mol/LMn(NO3)2 |
| DE-21# | Mg-ZSM-5 | 0.6mol/L Mg(NO3)2 |
| DE-22# | Mn,Mg-ZSM-5 | 0.2mol/LMn(NO3)2+0.4mol/L Mg(NO3)2 |
| DE-23# | Cu,Mn-ZSM-5 | 0.2mol/L Cu(NO3)2+0.2mol/L Mn(NO3)2 |
| DE-24# | Cu,Ce-ZSM-5 | 0.4mol/L Cu(NO3)2+0.2mol/L Ce(NO3)3 |
Embodiment 3: the preparation of bifunctional catalyst
The alkaline molecular sieve H-1 that embodiment 1 is prepared#~H-6#At least one of and embodiment 2 obtained in take off
Hydrogen catalyst DE-1#~DE-24#At least one of mixing, molding is broken, screening is 20~40 mesh, obtained double-function catalyzing
Agent number is CAT-1#~CAT-40#.Wherein CAT-1#~CAT-20#It is alkaline molecular sieve and dehydrogenation respectively in ball milling
Ball milling 10h (CAT-1 on machine#~CAT-5#)、15h(CAT-6#~CAT-15#)、20h(CAT-16#~CAT-20#), it is equal through mixing
After even, then formed；CAT-21#~CAT-40#After mixing for alkaline molecular sieve and dehydrogenation, on ball mill
Ball milling 10h (CAT-21#~CAT-25#)、15h(CAT-26#~CAT-35#)、20h(CAT-36#~CAT-40#) carry out into again
Type.
Gained bifunctional catalyst number and its contained alkaline molecular sieve and dehydrogenation type, the relationship of mass ratio
As shown in table 5.
Table 5
| Number | Bifunctional catalyst type, mass ratio | Number | Bifunctional catalyst type, mass ratio |
| CAT-1# | H-1#:DE-7#=2:1 | CAT-21# | H-3#:DE-11#=6:1 |
| CAT-2# | H-2#:DE-7#=2:1 | CAT-22# | H-3#:DE-12#=6:1 |
| CAT-3# | H-3#:DE-7#=2:1 | CAT-23# | H-8#:DE-13#=8:1 |
| CAT-4# | H-4#:DE-7#=2:1 | CAT-24# | H-8#:DE-14#=8:1 |
| CAT-5# | H-5#:DE-7#=2:1 | CAT-25# | H-8#:DE-15#=8:1 |
| CAT-6# | H-6#:DE-7#=2:1 | CAT-26# | H-8#:DE-16#=8:1 |
| CAT-7# | H-7#:DE-7#=2:1 | CAT-27# | H-8#:DE-17#=8:1 |
| CAT-8# | H-8#:DE-7#=2:1 | CAT-28# | H-8#:DE-18#=8:1 |
| CAT-9# | H-9#:DE-7#=2:1 | CAT-29# | H-8#:DE-19#=8:1 |
| CAT-10# | H-10#:DE-7#=2:1 | CAT-30# | H-8#:DE-20#=10:1 |
| CAT-11# | H-3#:DE-1#=4:1 | CAT-31# | H-8#:DE-21#=10:1 |
| CAT-12# | H-3#:DE-2#=4:1 | CAT-32# | H-8#:DE-22#=10:1 |
| CAT-13# | H-3#:DE-3#=4:1 | CAT-33# | H-8#:DE-23#=10:1 |
| CAT-14# | H-3#:DE-4#=4:1 | CAT-34# | H-8#:DE-24#=10:1 |
| CAT-15# | H-3#:DE-5#=4:1 | CAT-35# | H-3#:DE-7#=1:2 |
| CAT-16# | H-3#:DE-6#=6:1 | CAT-36# | H-8#:DE-7#=1:2 |
| CAT-17# | H-3#:DE-7#=6:1 | CAT-37# | H-3#:DE-1#:DE-7#=8:1:1 |
| CAT-18# | H-3#:DE-8#=6:1 | CAT-38# | H-3#:DE-7#:DE-17#=8:1:1 |
| CAT-19# | H-3#:DE-9#=6:1 | CAT-39# | H-3#:DE-7#=4:1 |
| CAT-20# | H-3#:DE-10#=6:1 | CAT-40# | H-3#:DE-7#=4:1 |
1 catalyst preparation of comparative example
The H-3 obtained by embodiment 1#And H-6#Alkaline molecular sieve is directly used as comparative catalyst, is crushed, sieves after molding
For 20~40 mesh, number CAT-D1#And CAT-D2#。
Embodiment 4: evaluating catalyst
It is anti-that the catalyst that 1g embodiment 3 prepares bifunctional catalyst and prepared by comparative example 1 is packed into small fixed respectively
It answers in device, and loads quartz sand at both ends.Catalyst 550 DEG C of activation 1h first under the He atmosphere of 40mL/min flow velocity, then
It is cooled to reaction temperature, raw material toluene is passed through with micro feed pump and methanol is reacted, toluene and methanol raw materials components mole ratio, sky
Speed, reaction pressure, reaction temperature are shown in Table 6.Product ventilation chromatography is analyzed, and reaction result is listed in table 6.
Table 6
It can be seen that bifunctional catalyst provided by the present invention by above embodiments result, be used for toluene and methanol system
When standby styrene reaction, toluene conversion, use ratio of methanol, styrene yield in product can be improved.
The above is only several examples of the invention, not does any type of limitation to the present invention, although of the invention
It is disclosed as above, however is not intended to limit the invention, any person skilled in the art with preferred embodiments, do not departing from this
In the range of inventive technique scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to equivalent reality
Scheme is applied, is belonged within the scope of technical solution of the present invention.
Claims (10)
1. a kind of method that methanol anaerobic dehydrogenation and Benzyl Side-Chain alkylation coupling reaction prepare styrene, which is characterized in that extremely
Less include: that the unstripped gas containing methanol and toluene is passed through reactor, contacted with catalyst, reacts, prepare the styrene；
The catalyst includes dehydrogenation and alkaline molecular sieve；
The molar ratio of toluene and methanol is 0.1~10:1 in the unstripped gas；The reaction temperature is 300~600 DEG C, reaction pressure
Power is 0.1~10MPa；The toluene and methanol feedstock gas gross mass air speed are 0.1~6h-1。
2. the side that methanol anaerobic dehydrogenation according to claim 1 and Benzyl Side-Chain alkylation coupling reaction prepare styrene
Method, which is characterized in that the molar ratio of toluene and methanol is 0.2~9:1 in the unstripped gas；The reaction temperature is 350~500
DEG C, reaction pressure is 0.1~2MPa；The toluene and methanol feedstock gas gross mass air speed are 0.2~5h-1。
3. the side that methanol anaerobic dehydrogenation according to claim 1 and Benzyl Side-Chain alkylation coupling reaction prepare styrene
Method, which is characterized in that include that at least one contains the catalyst bed of the catalyst in the reactor.
4. the side that methanol anaerobic dehydrogenation according to claim 1 and Benzyl Side-Chain alkylation coupling reaction prepare styrene
Method, which is characterized in that the mass ratio of the alkaline molecular sieve and dehydrogenation is 0.1~10:1；
Preferably, the mass ratio of the alkaline molecular sieve and dehydrogenation is 0.5~5:1.
5. the side that methanol anaerobic dehydrogenation according to claim 1 and Benzyl Side-Chain alkylation coupling reaction prepare styrene
Method, which is characterized in that the dehydrogenation is selected from alkali metal infusibility salt, load metal oxide, metal ion exchanged
At least one of molecular sieve.
6. the side that methanol anaerobic dehydrogenation according to claim 5 and Benzyl Side-Chain alkylation coupling reaction prepare styrene
Method, which is characterized in that the mass loading amount of metal oxide is 10~30% in the load metal oxide.
7. the side that methanol anaerobic dehydrogenation according to claim 5 and Benzyl Side-Chain alkylation coupling reaction prepare styrene
Method, which is characterized in that the alkali metal infusibility salt is alkali metal infusibility salt compound by grinding, dries, roasting, obtains described
Alkali metal infusibility salt；
The alkali metal infusibility salt compound is selected from least one of sodium carbonate, Boratex, sodium molybdate；
The carrier of the load metal oxide is SiO2, metal oxide is selected from the oxide of copper, the oxide of silver, zinc
At least one of oxide, oxide of zirconium；
Metal ion is selected from sodium ion, copper ion, cerium ion, manganese ion and magnesium ion in the molecular sieve of the metal ion exchanged
At least one of；The molecular sieve is ZSM-5 molecular sieve.
8. the side that methanol anaerobic dehydrogenation according to claim 1 and Benzyl Side-Chain alkylation coupling reaction prepare styrene
Method, which is characterized in that at least one in the alkali molecules FAU structure molecular screen modified screened from alkali metal ion exchange
Kind；Wherein, in the modified FAU structure molecular screen of the alkali metal ion exchange, the exchange degree of alkali metal ion is 20~90%；
Preferably, the sial atomic molar ratio of the FAU structure molecular screen is 1~10；
The alkali metal ion is selected from least one of potassium ion, rubidium ion, cesium ion；The FAU structural molecule is screened from X
At least one of type molecular sieve, Y type molecular sieve.
9. the side that methanol anaerobic dehydrogenation according to claim 1 and Benzyl Side-Chain alkylation coupling reaction prepare styrene
Method, which is characterized in that the preparation method of the catalyst at least includes the following steps:
(a) dehydrogenation is obtained；
(b) alkaline molecular sieve is obtained；
(c) it by dehydrogenation and alkaline molecular sieve ball milling 2~20 hours on ball mill respectively, remixes and is uniformly catalyzed
Agent molding；Or
By the mixture containing dehydrogenation and alkaline molecular sieve, catalyst is carried out again within ball milling 2~20 hours on ball mill
Molding.
10. the preparation method of bifunctional catalyst according to claim 9, which is characterized in that dehydrogenation described in step (a)
At least one of alkali metal infusibility salt, load metal oxide, the molecular sieve of metal ion exchanged are selected from catalyst；
The preparation method of the load metal oxide includes deposition-precipitation method or equi-volume impregnating；
The preparation method of the molecular sieve of metal ion exchanged includes: to utilize metal salt precursor solution pair in the dehydrogenation
After molecular sieve carries out ion exchange, through separation of solid and liquid, washing, drying, roasting, the molecular sieve of the metal ion exchanged is obtained；
The preparation method of alkaline molecular sieve described in step (b) includes: to be carried out using alkali metal salt precursor solution to molecular sieve
After ion exchange, through separation of solid and liquid, washing, drying, roasting, the alkaline molecular sieve is obtained.
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